Preparation and purification of perylene-3,4-dicarbimides

Abstract

PCT No. PCT/EP96/00117 Sec. 371 Date Jul. 21, 1997 Sec. 102(e) Date Jul. 21, 1997 PCT Filed Jan. 12, 1996 PCT Pub. No. WO96/22331 PCT Pub. Date Jul. 25, 1996Preparation of perylene-3,4-dicarbimides by reaction of a perylene-3,4,9,10-tetracarboxylic acid or of the corresponding anhydrides with a primary amine by performing the reaction in the presence of a tertiary nitrogen base as solvent and of a transition metal or transition metal salt as catalyst, and purification of perylene-3,4-dicarbimides obtained by reaction of a perylene-3,4,9,10-tetracarboxylic acid or of the corresponding anhydrides with a primary amine by heating the crude products initially in N-methylpyrrolidone and then treating the resulting N-methylpyrrolidone adducts in the presence of an organic diluent with a base, and if desired subjecting the subsequently isolated products to an additional treatment with an aqueous acid, and also novel perylene-3,4-dicarbimides and their use as fluorescent dyes, pigments or pigment additive precursors.

We claim: 
     
       1. A process for preparing perylene-3,4-dicarbimides by reacting a perylene-3,4,9,10-tetracarboxylic acid or the corresponding anhydrides with a primary amine, which comprises performing the reaction in a reaction medium consisting essentially of a tertiary nitrogen base as solvent and of a transition metal or transition metal salt as catalyst. 
     
     
       2. A process as claimed in claim 1, wherein the tertiary nitrogen base used is a nitrogen-containing heteroaromatic. 
     
     
       3. A process as claimed in claim 1, wherein the catalyst used is zinc, a zinc salt, copper, a copper salt or a mixture thereof. 
     
     
       4. A process for purifying perylene-3,4-dicarbimides obtained by reaction of a perylene-3,4,9,10-tetracarboxylic acid or of the corresponding anhydrides with a primary amine, which comprises first heating the crude products in N-methylpyrrolidone, then treating the resulting N-methylpyrrolidone adducts with a base in the presence of an organic diluent, and, if desired, subjecting the subsequently isolated products to an additional treatment with an aqueous acid. 
     
     
       5. A process as claimed in claim 4, wherein the base used is an alkali metal hydroxide or an alkali metal alkoxide. 
     
     
       6. A process for making pure perylene-3,4-dicarbimides by reacting a perylene-3,4,9,10-tetracarboxylic acid or the corresponding anhydrides with a primary amine, which comprises performing the reaction in the presence of a tertiary nitrogen base as solvent and of a transition metal or transition metal salt as catalyst and first heating the resulting crude products in N-methylpyrrolidone, then treating the resulting N-methylpyrrolidone adducts with a base in the presence of an organic diluent, and, if desired, subjecting the subsequently isolated products to an additional treatment with an aqueous acid. 
     
     
       7. Perylene-3,4-dicarbimides of the general formula Ia ##STR12## where R 1'   is C 14  -C 30  -alkyl whose carbon chain may be interrupted by one or more of --O--, --S--, --NR 3  --, --CO-- and/or --SO 2  -- and which is monosubstituted or polysubstituted by carboxyl, sulfo, hydroxyl, cyano, C 1  -C 6  -alkoxy or a 5-, 6- or 7-membered heterocyclic radical which is attached via a nitrogen atom and which may contain further heteroatoms and may be aromatic, where R 3  is hydrogen or C 1  -C 6  -alkyl; or R 1'   is C 5  -C 8  -cycloalkyl whose carbon skeleton is interrupted by one or more of --O--, --S--, and/or --NR 3  --; or R 1'   is phenyl which is polysubstituted by C 1  -C 4  -alkyl or methoxy at least in the two ortho positions, and/or monosubstituted or polysubstituted by C 5  -C 18  -alkyl, C 2  -C 6  -alkoxy, halogen, hydroxyl, cyano, carboxyl, --CONHR 4 , --NHCOR 4  and/or aryl- or hetaryl-azo, which may each be substituted by C 1  -C 10  -alkyl, C 1  -C 6  -alkoxy, halogen, hydroxyl, cyano or carboxyl, where R 3  is as above defined, and R 4  is hydrogen, C 1  -C 18  -alkyl, aryl or hetaryl, wherein the aryl or hetaryl may each be substituted by C 1  -C 6  -alkyl, C 1  -C 6  -alkoxy, halogen, hydroxyl or cyano, or R 1'  is naphthyl or hetaryl, which may each be substituted by a radical defined as substituents for phenyl, in which case the C 1  -C 4  -alkyl and C 1  -C 6  -alkoxy substituents may be in any desired position on the ring system; R 2  is in each instance independently of the other instances hydrogen; halogen; C 1  -C 18  -alkyl; aryloxy, arylthio, hetaryloxy or hetarylthio, which may each be substituted by C 1  -C 10  -alkyl, C 1  -C 6  -alkoxy, cyano or carboxyl.   
     
     
       8. Perylene-3,4-dicarbimides as claimed in claim 7 of the formula Ia where R 1'   is C 14  -C 30  -alkyl which is monosubstituted by carboxyl, sulfo, hydroxyl or a 5-, 6- or 7-membered heterocyclic radical which is attached via a nitrogen atom and which may contain further heteroatoms and may be aromatic; phenyl which is polysubstituted by C 1  -C 4  -alkyl at least in the two ortho positions, or monosubstituted or polysubstituted by halogen, hydroxyl, cyano, carboxyl, --COHNR 4  or --NHCOR 4  and/or monosubstituted by aryl- or hetaryl-azo, which may each be substituted by C 1  -C 10  -alkyl, C 1  -C 6  -alkoxy, halogen, hydroxyl, cyano or carboxyl; hetaryl which may be substituted by the radicals defined as above substituents for phenyl and/or by C 1  -C 4  -alkoxy, in which case the C 1  -C 4  -alkyl substituents may be in any desired position on the ring system;   R 2  is in each instance independently of the other instances hydrogen, halogen or phenoxy which may be substituted by C 1  -C 6  -alkyl, C 1  -C 6  -alkoxy, cyano or carboxyl.   
     
     
       9. Perylene-3,4-dicarbimides as claimed in claim 7 of the formula Ia where R 1'   is C 14  -C 30  -alkyl which is monosubstituted by carboxyl, sulfo or hydroxyl; phenyl which is substituted by C 1  -C 4  -alkyl in both ortho positions, hydroxyl, cyano, carboxyl, --CONHR 4  or --NHCOR 4 , where R 4  is C 1  -C 4  -alkyl or phenyl which may be substituted by C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy or cyano, or by phenyl- or naphthyl-azo which may be substituted by C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy, hydroxyl or cyano; monocyclic hetaryl which may be monosubstituted or polysubstituted by C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy, hydroxyl or cyano or monosubstituted by phenyl- or naphthyl-azo which may be substituted by C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy, hydroxyl or cyano; R 2  is in each instance independently of the other instances hydrogen or phenoxy which may be substituted by C 1  -C 4  -alkyl.   
     
     
       10. A method of coloring comprising contacting the perylene-3,4-dicarbimides of the formula Ia as set forth in claim 7 with an organic or organic/inorganic composite material.